DE2038659A1 - Paints based on resins and divinyl compounds and paint processes - Google Patents

Description

FORD-Werke Aktiengesellschaft Cologne-Deutz

Paints based on resins and divinyl compounds, as well as painting methods

According to the invention, a substrate is coated with a film-forming composition which consists essentially of new divinyl compounds and an α, β-olefinically unsaturated paint binder resin with a molecular weight of more than about 1000, preferably in the range from about 2000 to about 20,000, and the coating converted into a tenacious, solvent-resistant, wear-resistant and weather-resistant coating by exposing the coated substrate to ionizing radiation, preferably in the form of an electron beam. The new divinyl compounds are produced by reacting a monoepoxide with aoryl acid and / or methacrylic acid and then reacting the resulting monovinyl ester condensation product with an aoyl halide with tinyl unsaturation.

The invention is also concerned with the field of coatings. In particular, the invention relates to a method for coating a base made of hole, glass, metal or polymer

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Solids with a film-forming solution, the new! ^ Vinyl compounds and an in a, ß-position olefinic contains unsaturated paint, and crosslinking this film-forming solution to an abrasion-resistant, weather-resistant, solvent-resistant, viscous adhesive Film by exposing the coating to ionizing radiation, preferably in the form of an electron beam, and paints for this process.

The term "paint" as used herein includes both the binder including pigment and / or pulverized material Filler, the binder without OPigment and / or filler or only with a very low content on this, and it can optionally be colored. Thus, it can eventually be caused by ionizing radiation crosslinked paint binders may be the total or virtually all of the material used to form the Film was used, or it can be the carrier for pigments and / or particulate film material.

In the reaction scheme below, both the first reaction stage and the second reaction stage for the preparation of the divinyl compounds used according to the invention are listed.

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109808/2107

All starting materials for the preparation of the divinyl compounds monoepoxides used according to the invention. are monoepoxides with 4 "to 12 carbon atoms. In the In a preferred embodiment, the monoepoxide consists of a monocyclic monoepoxide with 7 to 10 carbon atoms according to the lOrmel

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wherein R is an aryl, alkylaryl, arylalkyl, aryloxy radical, means a cycloaliphatic or heterocyclic radical, for example vinyl glycidyl ether, vinyl cyclohexene epoxide, Vinyl cyclopentene epoxide, styrene epoxide, vinyl toluene epoxide, Vinylpyrid <ylepoxyd and the like .. With this one In the embodiment, the monoepoxides have a molecular weight in the range from about 112 to about 151.

In a further embodiment, the monoepoxide consists of a monocyclic monoepoxide with 5 to 6 carbon atoms, wherein the epoxy group is bonded to the carbon atoms of the cyclic structure, for example cyclohexene epoxide and cyclopentene epoxide. The monoepoxides of this group have molecular weights ranging from about 74 to about 98

In a third embodiment, the monoepoxide consists of an acyclic, aliphatic α, β-monoepoxide with 4 to 12 carbon atoms, for example 1-butene epoxide, 1-hexene epoxide, 1-dodecene epoxide and the like.

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The acyl laalogenides with vinyl unsaturation are preferred from acryloyl chloride and / or methaoryloyl chloride, but other compounds can also be used, for example the corresponding bromides.

The divinyl compounds used herein are homopolymerizable and monovinyl monomers, for example styrene, Yinyltoluol, a-methyl styrene, methyl methacrylate, Ä'thylacrylat, Butylaorylat, butyl methacrylate, hydroxypropyl methacrylate, Glycidylmethaorylat, 2-ethylhexyl acrylate and the like., Divinyl monomers such as divinylbenzene, to the epoxide by the reaction of a di with a molecular weight below about 2000, preferably in the range from about HO to about 500, with two molar proportions of acrylic acid and / or methacrylic acid and subsequent reaction of the ester condensation product obtained with two molar proportions of a saturated acyl halide, for example acetyl chloride, butyric acid chloride, hexanoic acid chloride , Capric acid chloride, stearic acid chloride, or a practically saturated aoyl halide, for example bsneoyl chloride, the divinyl reaction product obtained by reacting a molar proportion of a diepoxide with the molecular weight range given above with two molar proportions of acrylic acid or methaoryl acid and aneolytic substitution of the trivalent ester condensation product or two molar proportions of an α, B-position olefinically unsaturated aoyl halide with an aromatic residue on the carbon atom of the olefin bond, divide-by-sulfide cinnamon acid Unity of an aolartn Anttil «s ink Diepoiyda

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in the molecular weight range listed above with two molar proportions of acrylic acid and methacrylic acid and subsequent reaction of the ester condensation product obtained tetravinyl reaction product obtained with two molar proportions of an AcyInalogenide with Yinyi unsaturation, in. α, β-position olefinically unsaturated Polymers and. like., copolymerizable.

The Divinyladdukte used herein have lower viscosities than the corresponding monovinyl compounds, W which are obtained by reacting one mole of monoepoxide with acrylic acid or methacrylic acid. They are also more soluble in organic solvents and more sensitive to ionizing radiation. ! The type of divinyl compounds achieves good adhesion and the appropriate molecular weight for use can easily be achieved with the resin and, if necessary, with other monovinyl compounds »

The paint binder resins which are olefinically unsaturated in the α-position have molecular weights of more than about 1000, preferably in the range from about 2000 to about 20,000. They consist essentially of carbon, hydrogen and oxygen, but can also, if desired, have unsaturated substituents , for example · halogen atoms, nitrogen atoms and the like substituted stin. Advantageously, the concentration of the olefinic non-saturation in the α, β-position is reduced to about 0.5 to about 5, preferably 0.7 to about 5 units per 1000 units of the molecular weight. They are preferably made either from polyesters or from vinyl monoMsr ·. containing copolymers. "Suitable in

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For example, α, β-unsaturated resins are described in U.S. patents 3,437,512, 3,437,513, and 3,437 5H.

According to the invention, there is the paint binder without taking into account non-polymerizable solvents, pigments and particulate! mineral Filler consisting essentially of about 10 to about 80, preferably about 20 to about 60 parts by weight of (

Divinyl compound and correspondingly about 90 to about 20, preferably about 80 to about 40 parts by weight of the in α, β-position of olefinically unsaturated resin. It is within the scope of the invention a minor part, i.e. up to to an amount below about 50 wt .- # of the divinyl compound and / or the resins unsaturated in the α, β position by monovinyl monomers and / or a different divinyl compound, which essentially consists of carbon, Consists of hydrogen and oxygen and has a molecular weight below about 2600, preferably about 220 to about 1100, more preferably between about 220 and about 650 and / or a tetravinyl compound, which consists essentially of carbon, hydrogen and oxygen * and a molecular weight below about 2600, preferably between about 220 and about 1100, more preferably between about 220 and about 650 has to replace. These divinyl compounds and tetravinyl compounds are derived from the diepoxides listed above and are used for this purpose.

Those formed from the paint according to the invention Films can sometimes be viewed at relatively low

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at temperatures, for example between about 20 and about 7CPC hard «.. The radiant energy is in doses from about 0.1 to about 100 Mrads per second, preferably moving workpiece applied until the moist film is transferred to the tack-free state or “until the Film has received the desired dosage.

The abbreviation "rad" used here means a dose of radiation that absorbs 100 ergs of energy per gram of the absorber, for example the coating film. The abbreviation "Mrad" means 1 million rad. The electron emitting device can be an electron linear accelerator, which is used to develop a direct current potential in the Range of about 100,000 to about 500,000 volts is suitable. In such a device, the electrons usually emitted by a hot thread and accelerated by a uniform increase in tension. Of the Electron beam »which can be about 4 mm (1/8 inch) in diameter at this point, can then become a funnel-shaped beam and then through a metal window, for example made of a magnesium-thorium alloy, Aluminum, an alloy of aluminum and a small amount of copper, and the like, from a thickness of about 0.007 cm.

The term "ionizing radiation" as used herein means radiation of sufficient energy to cause polymerization of the oncoming films under consideration here, i.e. energies equivalent to about 5000 electron volts or larger. The preferred method of curing

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of the films of the present paints on substrates to which they are coated, is that such films are exposed to a beam of polymerization initiating electrons having an average energy in the range of about 100,000 to about 500,000 electron volts. When such a beam is used, it is preferred to use a minimum of 25,000 electron volts for every 2.5 cm of distance between the point of emission and the workpiece when the space is occupied by air. A corresponding setting (

can take place according to the relative resistance of the gas in between, which preferably consists of an oxygen-free inert gas such as hydrogen, nitrogen or helium.

The film-forming material advantageously has a sufficiently low application viscosity to permit rapid application to the substrate in a practically more uniform manner, and a sufficiently high viscosity that a PiIm of at least 25 M (0.001 inch) is maintained on the vertical surface without sagging will. The films are usually applied at an average * depth of about 2.5 to about 100 Ai with suitable adjustment of the viscosity and the application method *. Of course, the viscosity of the film-forming material obtained can be varied by choosing the divinyl compound and the further polymerizable compounds in the paint binder. Similarly, the viscosity of the film-forming composition by ZuactE of not polyaerisierbaren volatile solvents, for example toluene, xylene and acetone ₁ can

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The like. Be regulated that quickly after the application can be evaporated. With one or more such settings, the viscosity of the paint binder solution for application can be adjusted according to conventional paint application procedures, for example Spraying on, orphan application and the like is preferably applied to the pad as a continuous Film applied from practically even depth and cured on top.

The following examples serve to further illustrate the invention.

example 1

A DiyinylTorblndung was, in the following manner aue the materials listed manufactured ι

1. The following materials were placed in a reaction vessel equipped with a condenser, stirrer, nitrogen inlet and thermometer:

Materials Qewlohta parts

(a) Vinyloyclohexene epoxide 126

(b) methacrylic acid 85 (o) toluene (solvent) 500 (d) Diaethylbenzylanine (catalyst) 2

2. The Vinyloyclohexenepoxyd, the methacrylic acid and the Diaethylbeniylaaln were intimately mixed and partially au Toluene added, which was kept under nitrogen at 9CKl became.

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3. The reaction mixture was kept at € 90 until the reaction of the epoxy groups was practically complete, which was achieved by an acid number of the product of less than about 10 was determined.

4. The solvent was removed in vacuo.

5. The reaction product according to (4) was dissolved in an amount of 210 parts by weight in 500 parts by weight of toluene and 95 parts by weight of methacryloyl chloride was added dropwise to the held at 65 ⁰ C the reaction mixture was added until the HOL ceased Entwioklung .

6. The solvent was removed in vacuo and the divinyl connection gained.

In general, the reaction to prepare the new divinyl compound takes place both with regard to the first reaction stage and the second reaction stage at moderately elevated temperatures, preferably in the range from 40 to 100 ³ C, and in the presence of an alkaline or basic catalyst, for example an aromatic amine .

An α, β-olefinically unsaturated vinyl resin, Resin A.

was made in the following way:

Execution materials woven parts

Xylene 600

Methyl methacrylate 196

Ethyl acrylate 333,

Glyoidyl methacrylate 71

Azobisisobutyronitrile 6

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Weight parts 12th ο, 42 96 ο,

Execution materials
Hydroquinone
Methacrylic acid
Triethylamine

procedure

Xylene was used as a solvent in one with a stirrer), an addition funnel, a thermometer, a nitrogen

^ inlet pipe and a cooler equipped piston introduced. The amount of xylene is equal to the total weight of the vinyl monomers to be added. The xylene is heated to reflux and nitrogen bubbled through a solution during the heating and reaction. The combined monomers, were, with the exception of the methacrylic acid and the initiator (azobisisobutyronitrile), to the refluxed solution added evenly over 2 hours. The initiator weight was 10 parts by weight per 1000 parts by weight of the vinyl monomers. The reaction solution was refluxed until conversion of the monomers in the polymers was greater than 97%. In the second stage, hydroquinone was used as an inhibitor added and then the methacrylic acid for reaction with the

ψ Epoxy groups of the polymer added. As a catalyst, ^a triethylamine used. This esterification reaction was carried out at the reflux temperature until about 80 # esterification was achieved as determined by the residual acid number. The xylene was then removed by distillation in vacuo and the polymer was recovered.

Underlays made of wood, glass, metal and polymeric pesticides, ie polypropylene and acrylonitrile-butadiene-styrene copolymers, were essentially made with the paint binder

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OWGWAL INSPECTED

Vinyl compound and resin A-, using the the following procedure:

1. 20 parts by weight of the divinyl compound were mixed with 80 parts by weight of the resin A mixed and diluted to spray viscosity with acetone. This solution was based on the above documents at an average delivery of about 25 / u (O, OO1 inch) sprayed on and the solvent evaporated. The overdone Support was placed in a nitrogen atmosphere and at a distance of about 25 cm below the electron-emitting window of a cathode ray type electron accelerator through which an electron beam is applied to the coated Surface was projected until the wet coating was polymerized to the tack-free state. The electrons of the beam had an average energy of about 275,000 electron volts at a current of about 25 milliamperes .

2. A second group of documents has been coated in the above manner using the gleiohen conditions and materials, however, the applied arrival consisted λ striohsbinderlösung from 60 parts by weight of the ropes divinyl compound, 40 parts by weight of the resin A and acetone, the coating being applied at a rate of about 75 / u.

3. A third group of rootstocks was made in the catfish * given above using the same conditions and materials coated, but there was the applied anti-triobinder solution from 10 lines by weight of the divinyl compound, 90 parts by weight dts resins A and Aotton.

ORIGINAL INSPECTED

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4. A fourth group of documents was processed in the same way using the same conditions and materials. preferred, but "the paint binder solution used consisted of parts by weight of the divinyl compound, 20 parts by weight of Resin A. and acetone.

Excellent, strongly adherent and very permanent coatings were obtained.

Example 2

The procedure of Example 1 was followed with the following differences repeated: (a) the resin A was replaced with the polyester resin B shown below, (2) as the irradiation atmosphere Helium was applied; and (3) an electron beam with an average energy of about 350,000 electron volts was applied .

Manufacture of the resin B Starting materials parts by weight

Maleic anhydride 14.7

Tetrahydrophthalic anhydride 72.3

ITopentyl glycol 75.0

Dibutyltin oxide (catalyst) 7.06

procedure

The reactants were heated to approximately MCPC in a reaction vessel and held at this temperature for one hour. The temperature of the feedstock was then increased to 225 ⁰ C and t'etwa fcilaseen at this temperature until the acid number was of the obtained resin below about 20 »The Übereohuß of glycol and water were removed and then 0.03 parts by weight in vacuo Hydroquinone added when the acid number is

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- 15 half about 10 was.

The coatings obtained in this way also showed excellent properties.

Example 3

The procedure according to Example 2 was repeated, but the resin B was replaced by an equal amount by weight of the resin C, namely a polyester made by the process used to make resin B, but with one | equimolar amount of phthalic anhydride instead of tetrahydrophthalic anhydride was used.

Example 4

The procedure according to Example 2 was repeated, but the resin B was replaced by an equal amount by weight of the resin D, namely a polyester produced by the method used to produce the resin B, but with a equimolar amount of ethylene glycol instead of keopentyl glycol was used.

Example 5

The procedure of Example 2 was repeated, but the ( Resin B replaced by an equal amount by weight of Resin E, one after that used to make Resin B. Method made polyester, but using an equimolar amount of trimellitic anhydride instead of Tetrahydrophthalic anhydride was used.

Example 6

The procedure of Example 2 was repeated, but that Resin B replaced by an equal amount by weight of resin P,

ORIGINAL INSPECTED

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namely a polyester made by the process used to make resin B, but an equimolar amount of pentaerythritol instead of neopentyl glycol was used.

Example 7

The procedure of Example 2 was repeated, but the resin B by an equal amount of resin G by weight replaced, namely a polyester produced by the method used to produce the resin D, wherein but an equimolar amount of 1,6-hexamethylene glycol instead of neopentyl glycol was used.

Example 8

The procedure of Example 2 was repeated, but the resin B was replaced by an equal amount of the resin H, namely a polyester produced by the process used to produce resin B, but with an equimolar. Amount of! Fumaric acid instead of maleic anhydride was used.

Example 9

The procedure according to Example 2 was repeated, but the resin B was replaced by an equal amount by weight of the resin Έ, namely a polyester produced by the method used to produce resin B, but an equimolar amount of 2-butene-1,4-diol instead of neopentyl glycol was used.

The products of Examples 2 to 9 also showed excellent coatings.

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O'f

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Example 10

The procedures of Examples 1 and 2 were followed repeated by non-polymerizable solvents, but replacing acetone with toluene; became.

There was no difference in excellent properties the coatings.

Example 11

The procedure of Example 1 was repeated, but that Resin A replaced by a resin J composed of different vinyl monamers

Production of the resin J Starting materials parts by weight

Methyl methacrylate 400

ithylaorylate 400

Hydroxyethyl methaorylate 195

Toluene 1000

Benzoyl peroxide 30

procedure

Stage I. The benzoyl peroxide was dissolved in a solution of methyl methacrylate, ethyl acrylate and hydroxyethyl methaorylate and one half of the toluene. This solution was portionwise added to the remaining toluene at Hüokflußtemperatur for a period of 7 hours, with the abfliteeende, a bath temperature of about 138 - was 140V. Daa Srhititn to Rüokfluß was continued for a further 3 Stumdtn and dlt reading cooled.
Stage II.

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Loryloylochloride _; 53.8

Toluene. 30th

1 Ö'MOI / If 0 7 'ORlGlMAL 1NSPECT6D

The solution after stage I was set to 6CK! heated and a solution of AoryloylChlorid and! toluene was added dropwise over a period of 4 hours, wherein the temperature was allowed to rise wetwa 9O ³ C. Bs was heated for a further two hours and then the polymer was obtained by vacuum distillation.

Example 12

The procedure of Example 1 was repeated, but the resin A was replaced by a resin K composed of different vinyl monomers.
Production of the resin K

Starting materials parts by weight

Ethyl acrylate 39

Methyl methacrylate 24

Allyl alcohol 36

Benzoyl peroxide 1

Xylene (solvent)

procedure

Step I. a same Gewiohts ^ quantity of xylene was placed in a with condenser, thermometer, stirrer and drip * funnel equipped reaction vessel * as to be added to the first reaction stage reactants "introduced The xylene was at about 100 - heated 12O ^1C. The four reactants were mixed thoroughly and slowly added to the heated xylene over 4 hours with a dropping trio. The reaction mixture was kept at this temperature for one to two hours after the addition had ended and then cooled to room temperature. . \

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The second stage of the implementation was carried out with the following materials:

Stage II.

Starting materials lightweight parts

Copolymer according to level I 69 in xylene

Allyl glycidyl ether 30.8

Potassium hydroxide 0.2

The solution of the allyl glycidyl ether and potassium hydroxide became added to the copolymer at tree temperature. Then the mixture was brought to a temperature of about 100 ' - Heated 12CPC and maintained this temperature for 7 hours. The xylene was separated from the polymeric reaction product by distillation in vacuo.

The products of Examples 11 and 12 also showed excellent coatings.

Example 13

The procedures of Examples 1 and 2 were repeated, but vinyl glycidyl ether was used as the monoepoxide.

Example 14 |

The procedures of Examples 1 and 2 were repeated, however vinylcyclopentene epoxide was used as a monoepoxide.

example 15th

The procedures of Examples 1 and 2 were repeated, but the monoepoxide used was styrene epoxide.

Example 16

The procedures of Examples 1 and 2 were repeated, but vinyltoluene epoxide was used as the monoepoxide.

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Example 17

The methods of the B _e ispiele 1 and 2 were repeated, but as the monoepoxide Viny lpyr idyl epoxy d applied ".

Example 18

The procedures of Examples 1 and 2 were repeated, except that cyclohexene epoxide was used as the monoepoxide.

Example 19

fc The procedures of Examples 1 and 2 were repeated, however Cyclopentenepoxide was used as the monoepoxide.

Example 20

The procedures of Examples 1 and 2 were repeated except that the 1-Butenepoxyd was used as a monoepoxide.

Example 21

The procedures of Examples 1 and 2 were repeated, but 1-hexene epoxide was used as the monoepoxide.

Example 22

The procedures of Examples 1 and 2 were repeated, but 1-dodecene epoxide was repeated as the monoepoxide applied.

Also in Examples 13 to 22 are characterizing enteric coatings were obtained.

Example 25

The procedure of Example 1 was repeated, but methaoryloyl bromide was used instead of methacryloyl chloride .used.

109808/2107

Example 24

The process according to Example 1 was repeated, but a _o ryloyl chloride was used instead of methacryloylohlorid. ·

Example 25

The procedure of Example 1 was repeated, however Acrylic bromide was used instead of methacryloyl chloride.

Example 26

The process according to Example 1 was repeated, but the monoepoxide was initially used with acrylic acid instead of methacrylic acid implemented.

The products of Examples 23 "to 26 also showed excellent results Coatings.

Example 27

The process according to Example 1 was repeated, but in separate experiments smaller proportions of the divinyl compound and smaller proportions of the resin A were replaced by equal amounts by weight of monovinyl monomers and the substrates as in Example 1 were covered with the following differences:

The first group of documents was coated as in Example 1, but 49% by weight of the divinyl compound were replaced by an equal amount by weight of nonovinyl monomers, namely an equimolar mixture of methyl etha aylate, ityla aylate, batyl aylate and 2-ethyl ethyl ayla in the paint binder.

109801 / 21Of 'original inspected

Further documents were covered in the same way, however, in the paint binder solution 1 wt .- # of the divinyl compound was replaced by an equal weight amount of monovinyl monomers, namely methyl methacrylate and styrene in replaced with an equimolar mixture.

Further documents were covered in the same way, however, 25% by weight of the divinyl compound was added to the paint binder solution by an equal amount by weight of monovinyl monomers, namely an equimolar mixture of methyl methacrylate, ithylacrylate, butyl aorylate and styrene.

Further documents were covered in the same way, however, 1 wt .- # des Resin A replaced by an equal amount of styrene by weight,

Further documents were covered in the same way, however, 25 wt .- # des Resin A by an equal amount by weight of methyl methacrylate replaced.

Further documents were covered in the same way, however, in the paint binder solution, 49% by weight of resin A was replaced by an equal amount by weight of monovinyl monomers, i.e. an equimolar mixture of styrene and methyl methaorylate.

Example 28

The divinyl compound was prepared as in Example 1 and a tetrvinyl compound by the same procedure

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prepared by adding 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxymethylcyclohexanecarboxylate reacted with two molar equivalents of methacrylic acid and then the obtained divinyl ester condensation product was reacted with two molar equivalents of methacryloyl chloride.

The bases were then coated as in Example 1, except that 49% by weight of the Divinyl compound by an equal amount by weight of

Tetravinyl compound replaced. '

Further documents were covered in the same way, however, 1 wt .- ^ in the paint binder solution Divinyl compound replaced by an equal amount by weight of the tetravinyl compound.

Further bases were coated in the same way, except that 25% by weight of the Divinyl compound replaced by an equal amount by weight of the tetravinyl compound.

Further documents were coated in the same way, f however, in the paint binder solution 1 wt Resin A replaced by an equal amount by weight of the tetravinyl compound.

Further bases were coated in the same way, except that 25% by weight of 96 dew Resin A replaced by an equal amount by weight of the tetravinyl compound.

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Further bases were coated in the same way, but 49 wt .- ^ des in the paint binder solution Resin A by an equal amount by weight of the tetravinyl compound replaced.

Example 29

The divinyl compound was prepared as in Example 1, and a different divinyl using _k the same procedure by reacting a molar proportion of a diepoxide ™ which is 1-Epoxyäthyl-3,4-epoxycyclohexane, with two molar equivalents of methacrylic acid and subsequent reaction of the obtained Divinyl ester condensation product prepared with two molar equivalents of butyric acid chloride.

The bases were then coated as in Example 1, however were in the paint binder solution 49 wt .- ^ der aus Monoepoxide prepared divinyl compound by an equal amount by weight of the divinyl compound prepared from the diepoxide replaced.

% Further documents were coated in the same way,

however, in the paint binder solution, 1% by weight of the off the divinyl compound prepared from the monoepoxide by an equal amount by weight of the divinyl compound prepared from the diepoxide replaced.

Further documents were covered in the same way, however, 25% by weight of the Divinyl compound made from the monoepoxide by an equal amount by weight of that made from the diepoxide

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- 25 divinyl compound replaces

Further documents were covered in the same way, however, in the paint binder solution, 1% by weight of Resin A was replaced by an equal amount by weight of that of Diepoxyd produced divinyl compound replaced.

Other documents were coated in the same manner but were 25 percent in the paint binder solution -. $> Of the resin A replaced by an equal amount by weight of divinyl epoxy prepared from the di (.

Further documents were covered in the same way, however, in the paint binder solution, 49% by weight of the resin A was replaced by an equal amount by weight of that of the diepoxide produced divinyl compound replaced.

Example 30

The divinyl compound was prepared as in Example 1 and a different divinyl compound was used the same process by implementing a Diepoxyd, viz Dicyclopentadiene dioxide, with two molar equivalents of acrylic acid and subsequent conversion of the resulting Di- ™ vinyl ester condensation product with two molar equivalents Cinnamic acid chloride produced.

The bases were then coated as in Example 1, except that 49% by weight of the paint binder solution were obtained the divinyl compound produced from the monoepoxide by an equal amount by weight of that produced from the diepoxide Divinyl compound replaced »

Further documents were covered in the same way, however, 1 wt .- ^ in the paint binder solution Divinyl compound produced from the monoepoxide an equal amount by weight of the Diviny ^ compound produced from the diepoxyd replaced.

Further underlays were covered in the same way, however, 25% by weight of the divinyl compound prepared from the monoepoxide was carried out in the paint binder solution replaced an equal amount by weight of the divinyl compound prepared from the diepoxide.

Further bases were coated in the same way, except that 1% by weight of the resin was used in the paint binder solution A replaced by an equal amount by weight of the divinyl compound prepared from the diepoxide.

Other documents were coated in the same manner, but 25 wt .- ^ of the resin A was replaced by an equal weight amount of the divinyl compound prepared from the diepoxide in the paint binder solution.

Other documents were coated in the same manner, but 49 wt .- # of the resin A was replaced by an equal weight amount of the divinyl compound prepared from the diepoxide in the paint binder solution.

The coatings obtained according to Examples 27 to 30 also had excellent properties.

000/210 7

Example 51

The process of Example 30 was repeated, but using benzoyl chloride instead of cinnamic acid chloride in the preparation the divinyl compound from the diepoxyd is used.

Example 32

The procedure of Example 31 was repeated, but using stearic acid chloride instead of that in the preparation of the Divinyl compound used from the diepoxyd used cinnamic acid chloride.

Example 33

The procedure of Example 31 was repeated, but instead of hexanoic acid chloride in the preparation of the Divinyl compound used from the diepoxide used cinnamic acid chloride.

Example 34

The procedures of Examples 27 to 33 were repeated, but using polyester resin B instead of vinyl resin A.

Example 35

The procedure of Example 1 was repeated, but -f> the divinyl compound produced from the monoepoxide and 25 wt .- # of the resin A by an equal weight of an equimolar mixture of styrene and methyl methacrylate 25 wt. Replaces.

Example 36 The procedure of Example 2 was repeated, however

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25 wt .- # of the divinyl compound prepared from the monoepoxide and 25 wt .- # of Resin B by an equal amount by weight of an equimolar mixture of styrene and Replaced methyl methacrylate.

The products of Examples 31 "to 36 were also excellent Coatings on.

According to a preferred embodiment, a smaller amount of the resin which is olefinically unsaturated in the α, β-position is and / or a smaller amount of the new livinly compound replaced by an equal amount by weight of monovinyl monomers. The monovinyl monomers used are monomeric compounds with a terminal group ι used in which

-C = CH ₂

X represents a hydrogen atom or a methyl group; preferred examples of such monomers are vinylbenzene compounds, such as styrene, vinyl toluene, α-methylstyrene, acrylic acid or methacrylic acid esters, e.g. Methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate and similar connections.

109808/2107

The method according to the invention for covering a base, wherein a film-forming solution as a paint film on a Applied to the surface of the base and on it by exposure of the ■ coated surface to ionizing radiation is crosslinked, is that a film-forming solution is used, which regardless of non-polymerizable Solvents, pigments and particulate mineral filler consisting essentially of about 20 up to about 90 parts by weight of an α, β-olefinically unsaturated resin with a molecular weight of more than about 1000 and about 80 to about 10 parts by weight of a Divinyl compound consists, which by reacting a molar proportion of acrylic acid and / or methacrylic acid with a molar proportion of a monoepoxide and subsequent conversion of the resulting monovinyl ester condensation product with a molar proportion of an acyl halide with vinyl unsaturation » in particular acryloyl chloride or methacryloyl chloride.

According to the invention, blessings are obtained, consisting of a base and a polymerized coating of a paint formed on an outer surface of the same by applying a pilme to the surface at a practically uniform depth from a solution which forms a layer, which without consideration of non-polymerizable solvents, pigments and particulate! mineral filler consists essentially of about 20 to about 90 parts by weight of an α, β-olefinically unsaturated resin with a molecular weight in the range of about 1000 to about 20,000 and about 80 to about 10 parts by weight of a divinyl compound » what duroh ümaetaung a molar

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109808/2107 originally inspected

Part of a monoepoxide with a molar part of Acrylic acid and / or methacrylic acid and subsequent conversion of the resulting monovinyl ester condensation product with a molar proportion of an acyl halide with vinyl unsaturation, in particular acryloyl chloride or methacryloyl chloride and crosslinking of the film on the surface by ionizing radiation, in particular with an electron beam.

109808/2107

Claims (25)

- 31 -. . Claims 1. Paint that is polymerizable by ionizing radiation is characterized in that it does not take into account non-polymerizable solvents, pigments and particulate mineral filler consisting essentially of a film-forming solution of about 20% "up to about 90 parts by weight of one in the α, β-position olefinic unsaturated resin having a molecular weight greater than about 1,000 and from about 80 to about 10 parts by weight of one Divinyl compound consists, which by reacting a molar proportion of a monoepoxide with a molar proportion of acrylic acid and / or methacrylic acid and subsequent reaction of the resulting monovinyl ester condensation product with a molar proportion of an acyl halide with vinyl saturation. 2. A coating composition according to claim 1, characterized in that a monocyclic monoepoxide with 7 to 10 is used as the monoepoxide Carbon atoms according to the formula R-C-O-H I I HH wherein R is an aryl, alkylaryl, arylalkyl, aryloxy radical, means a cycloaliphatic or heterocyclic radical was used. 3. coating composition according to claim 1, characterized in that 109808/2107 ' as monoepoxide cyclohexene epoxide and / or cyclopentene epoxide was used. 4. coating composition according to claim 1, characterized in that that the monoepoxide is an acyclic aliphatic <x, ß-monoepoxide having 4 to 12 carbon atoms was used. 5. A coating composition according to claim 1 to 4 »characterized in that the resin which is olefinically unsaturated in the α, β-position about 0.5 to about 5 units of α, β olefinic saturation to 1000 units of molecular weight and has a molecular weight in the range of about 2000 to owns about 20,000. 6. A coating composition according to claim 1 or 2, characterized in that the resin which is olefinically unsaturated in α, β-position about 0.7 to about 3 units of olefinic α, β-unsaturation to 1000 units of molecular weight and has a molecular weight in the range of about '2000 to about 20,000 and a monocyclic monoepoxide with 7 to 10 carbon atoms correspondingly as monoepoxide the formula / \
RCCH A i wherein an aryl, alkylaryl, arylalkyl or aryloxy group or a cycloaliphatic or heterocyclic one Remainder means was used. 7 Paint composition according to Claims 1 to 6, characterized in that that the chloride or bromide of the acyl halide 1 09808/2107 - 33 Acrylic acid or methacrylic acid was used. 8. Coating composition according to claim 1 to 7, characterized daduroh, that a lower set of the α, ß-graduation olefinically unsaturated resin is replaced by an equal amount by weight of a monovinyl monomer. 9. Anstriohsmasse according to claim 1 to 7, characterized in that a minor amount of the divinyl compound is replaced by an equal amount by weight of monovinyl monomers (. 10. A coating composition according to claim 1 to 7, characterized in that a smaller amount of the α, ß-position olefinically unsaturated resin duroh an equal weight a tetravinyl compound which is essentially consists of carbon, hydrogen and oxygen and has a molecular weight below about 2600, in particular in the range of about 220 to about 1100, preferably about 220 to about 650 has, is replaced. 11. Anstriohsmasse according Anspruoh 1 to 7 »marked by a characterized in that a minor amount of the divinyl compound by an equal Gewiohtsmenge a Xetra vinyl compound consisting essentially of carbon, there is hydrogen and oxygen and having a molecular weight below about 2600, in particular in the range of about 220 to about 1100, preferably in the range from about 220 to about 650, is replaced. 12. Anstrioh mass according to claims 1 to 7 »daduroh marked, 109808/2107 2038653 that a smaller amount of the olefinic in the α, β-position unsaturated resin by an equal weight of a divinyl compound having a molecular weight below about 2600, especially from about 220 to about 1100 . is replaced, which is replaced by the reaction of a diepoxide with two molar equivalents of acrylic acid and / or methacrylic acid and subsequent reaction of the divinyl ester condensation product obtained with two molar proportions of a saturated acyl halide. 13. Coating composition according to claim 1 to 7 »characterized in that a smaller amount of the divinyl compound by an equal amount by weight of a divinyl compound having a molecular weight below about 2,600, especially in the range from about 220 to about 1100, which is replaced by reacting a diepoxide with two molar equivalents of acrylic acid and / or methacrylic acid and subsequent reaction of the divinyl ester condensation product obtained with two molar equivalents of a saturated acyl halide. 14 * Paints that can be polymerized by ionizing radiation is, in particular according to claim 1, characterized in that it is not polymerizable without taking into account en solvents, pigments and particulate) mineral filler consisting essentially of a film-forming Solution of about 40 to 80 parts by weight of a resin which is olefinically unsaturated in the α, β-position and has a molecular weight ranging from about 1,000 to about 20,000 and about 60 to about 20 parts by weight of a divinyl compound exists, which duroh implementation of a monoepoxide with 109808/2107 a molecular weight ranging from about 72 "to about with acrylic acid and / or methacrylic acid and subsequent reaction of the resulting monovinyl ester condensation product with an acyl halide with vinyl unsaturation. 15. Coating composition according to claim H, characterized in that that a smaller amount of the a, ß-position olefinically unsaturated Haraes by an equal weight weight Monovinyl monomers is replaced. ~ * " 16. A coating composition according to claim 14 »characterized in that that a smaller amount of the divinyl compound is replaced by an equal amount by weight of monovinyl monomers. 17. A coating composition according to claim H _f, characterized in that a smaller amount of the α, β-olefinically unsaturated resin and a smaller amount of the divinyl compound are replaced by equal amounts by weight of monovinyl monomers. 18. Coating composition according to claim 20, characterized in that, J that a smaller amount of the divinyl compound by an equal amount by weight of a tetravinyl compound with one Molecular weight in the range from about 220 to about 650 is replaced, which by conversion of a molar proportion of a diepoxide with two molar proportions of acrylic acid and / or methacrylic acid and subsequent implementation of the obtained ester condensation product with two molar proportions of an acyl halide with tinyl unsaturation, .ine- 109808/2107. particular acryloyl chloride or methacryloyl chloride became. 19 · Painting solution according to claim 14, characterized in that that a smaller amount of the olefinically unsaturated in the α, β-position Resin by an equal amount by weight of a tetravinyl compound with a molecular weight im Range from about 220 to about 650 is replaced, which by reacting a molar proportion of a diepoxide with two molar proportions of acrylic acid and / or methacrylic acid and subsequent conversion of the ester condensation product obtained with two molar proportions of an acyl halide with vinyl unsaturation, in particular acryloyl chloride or methacryloyl chloride. 20. Coating composition according to claim 14, characterized in that that a smaller amount of the divinyl compound by an equal amount by weight of a divinyl compound with one Molecular weight in the range from about 220 to about 650 is replaced, which by reaction in a molar proportion of a diepoxide with two molar proportions of acrylic acid and / or methacrylic acid and subsequent implementation of the obtained ester condensation product with two molar proportions of a saturated acyl halide. 21. A coating composition according to claim 14, characterized in that a smaller amount of the olefinically unsaturated in α, β-position Resin by an equal amount by weight of a divinyl compound having a molecular weight in the range from about 220 to about 650, which is replaced by implementation 1 09808/2107 of a molar. (Part of a diepoxide with two molars Proportions of acrylic acid and / or methacrylic acid and subsequent conversion of the ester condensation product obtained with two molar proportions of a saturated acyl halide. 22. Coating composition according to claim 14 »characterized in that that a smaller amount of the divinyl compound by an equal amount by weight of a dirinyl compound with one Molecular weight in the range from about 220 to about 65o is replaced, which by conversion of a molar proportion of a diepoxide with two molar proportions of acrylic acid and / or methacrylic acid and subsequent implementation of the obtained ester condensation product with two molar proportions of an acyl halide which is olefinically unsaturated in the | x, ß-position with one on the ß-carbon atom of the olefin bond bound aromatic residue was obtained. 23. A coating composition according to claim 14 »characterized in that a smaller amount of the olefinically unsaturated in α, β-position Resin by a kgleiohe weight of a Divinyl compound having a molecular weight in the range of about 220 to 650 is replaced by reaction a molar proportion of a Biepoxyds with two molar proportions of acrylic acid and / or methacrylic acid and attached Implementation of the ester condensation product obtained with two molar proportions of one in the α, β-position olefinically unsaturated acyl halides with one at ß-carbon atom the aromatic properties of the olefin bond are obtained became. 109808/2107 24. A method for coating a substrate, wherein a film-forming solution is applied as a paint film to a surface of the substrate and is crosslinked thereon by exposing the coated surface to ionizing radiation, characterized in that a film-forming solution is used which without taking into account non-polymerizable solvents , Pigments and particulate! mineral! filler consists essentially of about 20 to about 90 parts by weight of an α, β-olefinically unsaturated resin with a molecular weight of more than about 1000 and about 80 to about 10 parts by weight of a divinyl compound, which by reaction a molar percentage of acrylic acid and / or methacrylic acid halide was mixed with vinyl unsaturation, particularly acryloyl chloride or _e M thacryloylchlorid obtained with a molar proportion of a Monoepoxyds and subsequent reaction of the obtained Monovinylesterkondensationsproduktes with a molar proportion of an acylphenylalanine. 25. Utility item, consisting of a base and a polymerized coating of a paint formed on an outer surface of the same by applying a film to the surface in a practically uniform depth from a film-forming solution, which without taking into account non-polymerizable solvents, pigments and particulate] mineral The filler consists essentially of about 20 to about 90 parts by weight of a resin which is olefinically unsaturated in the α, β-position and has a molecular weight in the range of about 1000 to about 20,000 and about 80 to about 10 parts by weight of a divinyl compound, which by implementing a molar proportion of a 109808/2107 Monoepoxyds with a molar proportion of acrylic acid and / or Methacrylic acid and subsequent reaction of the resulting monovinyl ester condensation product in a molar proportion of an acyl halide with vinyl unsaturation, in particular Acryloyl chloride or methacryloyl chloride was obtained, and crosslinking of the film on the surface by ionizing Radiation, especially with an electron beam. 109808/2107